Use of liquid-crystal displays, and processes for the recycling thereof

ABSTRACT

The present invention relates to the use of liquid-crystal displays (LCDs), and to processes for the recycling thereof. The processes according to the invention are characterised in that the LCDs are employed at least partly as replacement for other raw materials. In general, the LCDs are thermally treated here at a temperature in the range from 900 to 1700° C.

The present invention relates to the use of liquid-crystal displays(LCDs), and to processes for the recycling thereof.

The number of LCDs produced and the average display area per displayhave been increasing continuously for years. Since LCDs have recentlyalso been employed in TV sets, significant growth rates can also beexpected in coming years.

Although the most important LCD applications, such as, for example, innotebooks, monitors and TV sets, are long-life products, disposal orrecycling plays an ever more important role. The disposal, usual in thepast, of electronic components to landfill is increasingly beingreplaced by recycling processes, in particular also in view of EUdirective 2002/96/EC “Waste Electrical and Electronic Equipment”(“WEEE”), according to which LCDs have to be removed and disposed of orrecycled.

There are three different alternatives for recycling:

-   1. The LCD is dismantled and the individual components are re-used    for the original product (for example recovery of the liquid    crystals or glass and the use thereof for the production of new    LCDs).-   2. The LCD is dismantled and the individual components are used in    other industries or for other products.-   3. Individual components, preferably removed components, of LCDs are    subjected to heat recovery. In this case, for example, incineration    of the plastics serves for energy recovery.

The recycling of LCD glass for the production of new LCDs is described,for example, in JP 2001/305501 A, JP 2001/305502 A, JP 2000/024613 A andJP 2001/337305 A. It is disadvantageous in this type of recycling thatthe glass always contains surface contamination and in addition has tobe sorted on collection, which is associated both with high technicalcomplexity and also with high costs since in general different glassesare employed for different applications. Thus, for example, soda-limeglasses, which generally melt in the region of 1000° C., are generallyemployed for STN (Super Twisted Nematic) LCDs, while borosilicateglasses, which generally melt in the region of 1300° C., are generallyused for TFT (Thin Film Transistor) LCDs.

A special process for the disposal of LCDs is operated by the Berlincompany “VICOR” in a pilot plant, in which the displays are separatedmanually from casing and electronic parts and the polarisation films andsubsequently shredded to a size of about 1 cm (EDV, Elektronikschrott,Abfallwirtschaft 1993, pp. 231-241). The liquid crystals are thendistilled off in the furnace in a nitrogen/argon atmosphere at a maximumof 400° C. and atmospheric pressure. After condensation thereof in acold trap, they are passed to final storage in an underground landfillsite. The furnace temperature must not exceed 600° C. during thetreatment since otherwise, owing to the molecular structure, there is arisk of dioxin formation. The other material fractions arising, namelyglass, plastic and circuit boards, as well as structural elements areprocessed further by conventional recycling methods. It isdisadvantageous in this process that the separation of the liquidcrystals, which on the one hand only make up a very small proportion byweight of the total display (about 1 kg of liquid crystals per ton ofdisplays) and on the other hand represent a mixture of a multiplicity ofdifferent individual substances, is technically very complex and alsovery expensive, especially as the liquid crystals are subsequentlydisposed of to landfill. Use of the recovered liquid crystals in newLCDs is uneconomic according to the state of the art today. This alsoapplies to a further process for the extraction of liquid crystals withsolvents, which is described in JP 2002/126688 A.

The plastics, such as, for example, casing parts, but also polarisationfilms and other films, are generally separated off and either subjectedto heat recovery or used for other products. Thermal recycling of suchplastics is described, for example, in JP 2002/159955 A.

Use of the individual components for other products is also known. Thus,“Stragβurger Aufbereitungsgesellschaft” in Hockenheim (SAG) uses aprocess for blowing LCDs to give foam glass (degree project:“Recyclingverfahren für Flüssigkristal/displays” [Recycling Processesfor Liquid-Crystal Displays], Prof. Paffrath, Prof. Schön, Scala,TU-Darmstadt, 1997-98). The displays used here originate principallyfrom production rejects. They are mixed, including the LC liquid, withflat glass and apparatus glass, shredded, ground to dust fineness with aparticle size of 40 μm and mixed with a blowing agent. Foam-glass beadshaving a diameter of from about 5 to 15 mm are subsequently blown atfrom 800 to 850° C. The finished material is similar to the knownexpanded clay from hydrocultures and can be used as lightweightaggregate, as filler, as heat insulation material, as carrier granulesor as absorption material in the construction industry, in horticultureand landscaping and in waste water technology.

Further processes for the removal of polarisation films by mechanicalremoval, incineration or gasification, with subsequent comminution ofthe glasses and the use thereof as glass substitute are described in JP2001/296508 A and JP 2001/296509 A. The disadvantage of these processesis that the glasses obtained therefrom are highly contaminated anddiffer greatly in composition. They can therefore only be employed forlow-value applications.

Thus, JP 2000/084531 A describes a process for the recycling of LCDs inwhich the LCDs are firstly comminuted to particle sizes of less than 10mm. The particles comminuted in this way are subsequently employed insmelting furnaces at 1200° C. for the removal of iron. Disadvantageousin this process are, in particular, the complex comminution of the LCDsto particle sizes of less than 10 mm and the restricted use for theremoval of iron.

In addition, energy consumption is increasing continuously, and greatefforts are being made worldwide to save energy. In particular inindustrial production, it is being attempted, in particular, to reducecosts and/or energy consumption by process simplifications, heatrecovery and/or through the replacement of raw materials.

On the basis of the known prior art, one of the objects of the presentinvention was therefore to search for economical processes for therecycling of LCDs which do not have the disadvantages known from theprior art. In particular, the complex separation of the liquid crystalsand/or the polarisation films and the complex sorting of the displaysinto different types of glass were to be avoided, taking into accountthe energy efficiency of the process. A further object of the presentinvention was to provide novel potential uses of LCDs.

Surprisingly, it has been found that it is possible to subject LCDs tomaterial recycling in a simple and in addition economical process.

The present invention thus relates to a process for the materialrecycling of LCDs which is characterised in that the LCDs are at leastpartly, preferably completely, employed as replacement for other rawmaterials. In general, the LCDs are thermally treated here at atemperature in the range from 900 to 1700° C., preferably from 1000 to1400° C. and particularly preferably from 1200 to 1400° C. The thermaltreatment here is carried out, in particular, at temperatures above1200° C. and thus at temperatures at which even high-qualityborosilicate glasses melt.

The term LCD in the present application is taken to mean a displaywhich, besides two glass plates, may also comprise at least thematerials arranged between the two glass plates, such as, for example,liquid crystals, transparent films and adhesives, as well as electroniccomponents connected to the display (for example electrodes). Theplastic casing, the backlighting and, where appropriate, the polariserfilms are generally separated off in advance and recycled separately.However, they can also be recycled directly with the other components inthe process according to the invention.

LCDs consist essentially of from 30 to 99.8% by weight of glass and from0 to 60% by weight of plastic film, and from 0.1 to 20% by weight ofelectronics and liquid crystals.

In the process according to the invention, the LCDs employed arepreferably used LCDs and LCDs from production rejects.

The term thermal treatment in the present application is taken to meanthe treatment of LCDs with supply of energy through energy carriers,such as, for example, gas, coal and oil, and/or utilising the heatenergy present in the LCDs. The thermal treatment is usually carried outin thermal treatment plants, such as, for example, power stations,gasification plants and incinerators, preferably incinerators, with theequipment necessary for this purpose, such as, for example, fixedfurnaces, smelting furnaces, open-hearth furnaces or rotary-tubefurnaces.

In a first preferred embodiment, the LCDs are employed withoutcomminution. It is advantageous in this embodiment that comminution ofthe LCDs, which is associated both with an additional technicalcomplexity and with additional costs, can be omitted. In a secondpreferred embodiment, the LCDs are comminuted. However, the nature andsize of the comminution is not important here. Thus, the LCDs can eitherbe broken, shredded or ground. Depending on the nature of thecomminution, the average size of the fragments here is in the region ofdecimetres (in the case of breaking), in the region of centimetres (inthe case of shredding) and in the region of millimetres (in the case ofgrinding).

The process according to the invention has the advantage that thecomplex separation of the liquid crystals is superfluous and that at thesame time the risk of the formation of toxic products, such as, forexample, dioxin, is avoided since all organic products are destroyed atthe high temperatures of the process according to the invention.

A further advantage of the process according to the invention is thatthe starting material can be employed in ground, shredded, broken and/oruncomminuted form.

In addition, the process according to the invention is an economicalprocess in which, in addition, material and, where appropriate,additionally also at least partial thermal recycling of the LCDs takesplace.

The material and, where appropriate, additional, at least partialthermal recycling according to the invention can be carried out here invarious preferred embodiments.

In a first preferred embodiment, the LCDs are melted selectively at atemperature in the range from 900 to 1400° C., preferably from 1200 to1400° C.

In this way, it is possible for even different types of glass, asemployed in the production of the displays, to be recycled together. Theglass is recovered in pure form, albeit partly as a mixture of soda-limeglass and borosilicate glass. In addition, the metal parts originating,for example, from the electrodes settle in this embodiment and can beseparated from the glass melt.

The procedure for carrying out selective melting processes in which thetemperature is increased successively and firstly the low-melting andthen the higher-melting parts are melted is known to the person skilledin the art.

The products obtained in this way are used in the building materialsindustry or in road construction, for example as insulating material oras bulking material.

In a second preferred embodiment, the LCDs are mixed with othermetal-containing products, such as, for example, metal-containingsludges and/or catalysts, and thermally treated at a temperature in therange from 1200 to 1400° C., preferably from 1250 to 1350° C.

The proportion of LCDs in the mixture as a whole here is preferably inthe range from 5 to 50% by weight.

In this embodiment, the LCDs are employed in order to bind the non-noblemetals, such as, for example, iron, lead, zinc and tin, present in themetal-containing products and to separate them from the noble metals.The noble metals in the present application include both the noblemetals in the narrower sense, such as, for example, gold, silver,platinum, mercury, rhenium, ruthenium, rhodium, palladium, osmium andiridium, and also the seminoble metals nickel, copper and cobalt. Themixture is preferably melted in melting crucibles, smelting furnaces orrotary-tube furnaces and then poured into crucibles. After cooling, themelt is broken. The lower part is metal-containing and essentiallycomprises the noble metals, whereas the upper part comprises the slagwith the non-noble metals. The part comprising the noble metals ispassed to metal recovery, and the slag comprising the non-noble metalsis used, for example, in road construction.

This embodiment has the advantage of economic efficiency since the LCDsin this embodiment replace at least some of the furnace sand usuallyemployed, which necessarily has to be added in this process in order tobind the non-noble metals. In addition, at least some, preferably all,of the electronic components of the LCDs can also be recycled in thisembodiment since, as explained above, separation and recovery at leastof the noble metals take place.

A further significant advantage is the high energy input through theplastic films present in the LCDs. This will be shown by the followingcalculation:

Typically, 1 tonne of LCDs is composed of: 830 kg of glass (83% byweight) 149 kg of plastic film (14.9% by weight) 20 kg of electroniccomponents (2% by weight) and 1 kg of liquid crystals (0.1% by weight).

This gives rise to the following energy consideration, in which only theglass and plastic fractions are taken into account:

Thus, for example, the calorific value of PE film is 46,000 kJ/kg. 150kg of plastic film give rise to a calorific value of 6,900,000 kJ. Theenergy requirement for melting 1 kg of used glass is in the range from3000 to 6500 kJ. Accordingly, melting 830 kg of glass requires 2,490,000to 5,395,000 kJ.

As this illustrative energy consideration shows, the calorific value ofthe plastic films exceeds the energy requirement for melting the glass,i.e. a plastic proportion of only 15% by weight is sufficient to meltthe LCD glass. Consequently, no additional energy requirement istheoretically necessary.

In addition, the energy input increases further with increasing plasticproportion, advantageously through introduction of the plastic casingtoo.

For the above-described process according to the invention for therecovery of noble metals, the use of LCDs as raw material and/or addedmaterial thus additionally gives rise to a reduction in the requisiteenergy, i.e. an energy saving compared with the use of furnace sand.

A further advantage of this embodiment is the fact that the plasticfilms present in the LCDs can be employed as reducing agent in order toreduce the metal-containing products. In the reductive melting ofmetal-containing ores or products for the recovery of crude metals,carbon-containing products, such as, for example, coal, are generallyadded. This is because the metals would be oxidised at the high melttemperatures without the addition of reducing agents and would firsthave to be reduced back to metals in an additional production step. Theuse of the carbon-containing plastic films present in the LCDs thusenables at least some, preferably all, of the carbon-containing productsusually added as reducing agent in this process to be replaced or saved.

In a third preferred embodiment, the LCDs are thermally treated as rawmaterial and/or added material in rotary-tube furnaces at a temperaturein the range from 1100 to 1300° C., preferably from 1150 to 1250° C. Thethermal treatment of the LCDs in rotary-tube furnaces preferably resultsin the formation of a protective film on the inner lining thereof.

The proportion of LCDs as raw material and/or added material in thecomposition as a whole is preferably in the range from 1 to 20% byweight here.

Rotary-tube furnaces generally have a chamotte lining, which is attackedby aggressive gases and substances during the incineration of industrialwaste. Consequently, these chamotte bricks have to be replaced atregular intervals. The addition of silicate-containing products, suchas, for example, sand, enables a protective film to form on the walls,which considerably increases the life of the chamotte lining.

Surprisingly, it has now been found that LCDs can also be used insteadof the silicate-containing products and likewise result in the formationof a protective film on the chamotte lining. In this way, it is possibleto employ LCDs in the rotary-tube furnaces as replacement materials forpurchased silicate-containing products, such as, for example, furnacesands. The use of the LCDs also results in this embodiment in areduction in the requisite energy, since the calorific value of theplastic films can also be utilised in this embodiment for melting theLCD glass.

The present invention thus also relates to the use of LCDs in thermaltreatment plants.

In the use according to the invention, the LCDs employed are preferablyused LCDs and LCDs from production rejects.

In a preferred embodiment, the LCDs are employed as raw material and/oradded material in thermal treatment plants. Particular preference isgiven to the use of LCDs in thermal treatment plants, in particularrotary-tube furnaces, for the formation of a protective film on theinner lining thereof.

In a further preferred embodiment, the LCDs are employed as energysupplier in the thermal treatment plants.

The present invention furthermore relates to the use of LCDs in metalrecovery. In a first preferred embodiment, the LCDs are employed as rawmaterial and/or added material in metal recovery. However, preference isfurthermore also given to the use of the LCDs as energy supplier inmetal recovery.

Particular preference is given to the use of the LCDs in the recovery ofnoble metals from compositions comprising a mixture of non-noble andnoble metals. These compositions can be either naturally occurringproducts, such as, for example, ores, or industrial products, such as,for example, catalysts, electrical or electronic scrap, metal-containingsludges and other compositions comprising a mixture of noble andnon-noble metals. In particular, the LCDs are used here as raw materialand/or added material employed, at least partly, instead of the furnacesand usually employed and/or the carbon-containing products employed.

The present invention is described in greater detail below withreference to working examples, but without being restricted thereto.

EXAMPLE 1 (SELECTIVE MELTING)

In each case, an STN-LCD and a TFT-LCD, consisting of the two glassplates, the two polarisation films and the liquid crystals, includingcoatings, are comminuted separately to a size of from about 1 to 3 cm.In each case, 100 g of each fraction are weighed out and subsequentlymixed. An aluminium-oxide gutter is attached at an angle of 200, and themixture is introduced onto the higher-lying part. Slow heating to 1400°C. is carried out using an oxygen burner. Individual parts of the LCDsbegin to melt from 950° C. with vigorous evolution of fumes and burningof the polarisation film and flow downwards in the gutter. The remainderonly starts to melt at 1200° C. and flow downwards in the gutter. Byadroit collection of the fractions, about 40% of STN glass, 40% of TFTglass and 20% of a fraction comprising a mixture of STN and TFT glasscan be obtained.

EXAMPLE 2 (METALLURGY)

The experiments are carried out in a horizontally lying, gas-firedfurnace having a diameter of about 3.5 m and a length of 4 m.

The LCD mixture employed in these experiments consists of about 40% ofTFT-LCDs and about 60% of STN-LCDs. The LCDs are mostly in unbroken formand also partly—due to transfer operations—in broken form, i.e. in sizesof from 10 to 50 cm in diameter. In some cases, the electronics arestill present on the LCDs. The LCDs originate essentially fromelectrical recycling companies who have dismantled, collected and storedthe LCDs.

Using a bucket wheel loader, the metal scrap, the LCD mixture, thefurnace sand and the added materials, including coal, are introducedinto a mixer with internal blades having a capacity of about 10 m³ andmixed slowly. The precise compositions are described in Table 1. Duringthis mixing operation, the LCDs break at least partly, so that themajority of the LCDs after mixing have a size of from 3 to 30 cm. Themixture is then introduced continuously via a conveyor belt into thefurnace pre-heated to about 500° C. and heated to about 1 350° C. overthe course of several hours and melted. The melt is then discharged intoa steel vessel or brick-lined trough. After cooling, the metal fractionwith the noble metals from the metal scrap and the copper componentspresent in the electronics can easily be separated from the slag, whichcomprises the glass fraction of the LCDs, the added furnace sand and theadded materials, by knocking.

The slag obtained meets all demands of road construction.

The following experiments are carried out: TABLE 1 Metal Furnace AddedTotal Experiment scrap LCDs sand materials amount No. [kg] [kg] [kg][kg] [kg] 1 3000 300 850 650 4800 2 3000 600 600 600 4800 3 3000 900 350550 4800 4 3000 1200 100 500 4800 5 3000 1350 0 450 4800

Experiment 6

4.8 t of the mixture of the composition in experiment 2 are introducedas a mixture completely into the cooled furnace and then slowly heatedto 1300° C. The soot forming in part is burnt directly at the same timethrough the addition of oxygen to the heating gas. No differencecompared with experiments 1 to 5 is observed with respect to the metalfraction and the slag formation.

Experiment 7

600 kg of the above LCDs, 3000 kg of metal scrap, 600 kg of furnace sandand 600 kg of added materials are introduced as individual componentscompletely into the cooled furnace and then slowly heated to 1300° C.The introduction only breaks the larger LCDs, while the smaller ones areonly broken to an insignificant extent. The soot forming in part isburnt directly at the same time through the addition of oxygen to theheating gas. No difference compared with experiments 1 to 5 is observedwith respect to the metal fraction and the slag formation.

Experiment 8

4.8 t of the mixture of the composition in experiment 2 are introducedas a mixture completely into the cooled furnace and then slowly heatedto 1400° C. The soot forming in part is burnt directly at the same timethrough the addition of oxygen to the heating gas. No differencecompared with experiments 1 to 5 is observed with respect to the metalfraction, and the slag formation is assessed subjectively as somewhatglass-like.

EXAMPLE 3 (INDUSTRIAL WASTE INCINERATOR)

176 (120 1) drums each containing about 100 kg of LCDs, i.e. in totalabout 18 t of LCDs, are employed. The LCDs here are mostly in unbrokenform, i.e. in sizes of from 10 to 50 cm in diameter. The mixture hereconsists of about 70% of TFT-LCDs and about 30% of STN-LCDs. In somecases, the electronics are still present on the LCDs. The LCDs originateessentially from electrical recycling companies who have dismantled,collected and stored the LCDs.

The industrial waste to be incinerated, such as, for example, acids,contaminated organic solvents or solids, is incinerated in a largeindustrial-waste rotary-tube incineration furnace having a diameter of3.5 m and a length of 11 m using gas at temperatures of from about 1200to 1300° C. The industrial waste present in the drums and the LCDs areintroduced into the upper part of the furnace by means of a grab. Sincethe furnace is kept constantly at a temperature of from 1200 to 1300°C., the drums burst immediately on introduction. The LCDs are introducedcontinuously over a period of 24 hours instead of the silicon- orsilicate-containing substances otherwise used, such as furnace sand orglass. The silicon- or silicate-containing substances form a protectiveslag skin (=protective layer) on the brick lining of the rotary-tubefurnace and thus protect the wall against chemical attack and rapidwear. The quality of the protective slag skin is assessed visually. Theslag skin formed by the LCDs introduced into the incineration furnacedoes not differ from the slag skin formed by the silicon- orsilicate-containing substances otherwise usually employed.

1. Process for the material recycling of LCDs, characterised in that theLCDs are at least partly employed as replacement for other rawmaterials.
 2. Process according to claim 1, characterised in that theLCDs are thermally treated at a temperature in the range from 900 to1700° C.
 3. Process according to claim 2, characterised in that the LCDsare melted selectively at a temperature in the range from 900 to 1400°C.
 4. Process according to claim 1, characterised in that the LCDs aremixed with other metal-containing products and thermally treated at atemperature in the range from 1200 to 1400° C.
 5. Process according toclaim 4, characterised in that the metal- containing products compriseat least some of the electronic components of the LCDs.
 6. Processaccording to claim 4, characterised in that the LCDs are employed inorder to bind the non-noble metals present in the metal-containingproducts and to separate them from the noble metals.
 7. Processaccording to claim 4, characterised in that the LCDs replace at leastsome of the furnace sand usually employed in this process.
 8. Processaccording to claim 4, characterised in that the plastic films present inthe LCDs are employed as reducing agent in order to reduce themetal-containing products.
 9. Process according to claim 4,characterised in that the plastic films present in the LCDs replace atleast some of the carbon-containing products usually added as reducingagent in this process.
 10. Process according to claim 1, characterisedin that the LCDs are thermally treated as raw material and/or addedmaterial in rotary-tube furnaces at a temperature in the range from 1100to 1300° C.
 11. Process according to claim 10, characterised in that theLCDs as raw material and/or added material result in the formation of aprotective film on the inner lining of the rotary-tube furnaces. 12.Process according to claim 10, characterised in that the LCDs replace atleast some of the silicate-containing compounds usually employed in thisprocess.
 13. Use of LCDs as raw material and/or added material inthermal treatment plants.
 14. Use of LCDs according to claim 13 as rawmaterial and/or added material in thermal treatment plants for theformation of a protective film on the inner lining thereof.
 15. Use ofLCDs as energy supplier in thermal treatment plants.
 16. Use of LCDs inmetal recovery.
 17. Use according to claim 16, characterised in that theLCDs are employed as raw material and/or added material.
 18. Useaccording to claim 16, characterised in that the LCDs are employed asreplacement for furnace sands and/or carbon-containing products.
 19. Useaccording to claim 16, characterised in that the LCDs are employed asenergy supplier.
 20. Use of LCDs according to claim 16, characterised inthat the LCDs are employed in the recovery of noble metals fromcompositions comprising a mixture of noble and non-noble metals.
 21. Useof LCDs according to claim 20, characterised in that the LCDs areemployed in the recovery of noble metals from ores.
 22. Use of LCDsaccording to claim 20, characterised in that the LCDs are employed inthe recovery of noble metals from catalysts, electrical or electronicscrap and metal-containing sludges.